CN107446231A - A kind of composite polyethylene material being modified jointly by graphene, CNT and fullerene and preparation method thereof - Google Patents
A kind of composite polyethylene material being modified jointly by graphene, CNT and fullerene and preparation method thereof Download PDFInfo
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- CN107446231A CN107446231A CN201710515921.5A CN201710515921A CN107446231A CN 107446231 A CN107446231 A CN 107446231A CN 201710515921 A CN201710515921 A CN 201710515921A CN 107446231 A CN107446231 A CN 107446231A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/10—Homopolymers or copolymers of propene
- C08L23/12—Polypropene
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/001—Conductive additives
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/002—Physical properties
- C08K2201/003—Additives being defined by their diameter
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/002—Physical properties
- C08K2201/004—Additives being defined by their length
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/002—Physical properties
- C08K2201/006—Additives being defined by their surface area
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/017—Additives being an antistatic agent
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/04—Antistatic
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Extrusion Moulding Of Plastics Or The Like (AREA)
Abstract
The present invention relates to macromolecule material preparation area, particularly a kind of composite polyethylene material being modified jointly by graphene, CNT and fullerene, the material includes following components：50 100 parts of polyethylene；0.1 1 parts of graphene；0.1 1 parts of CNT；1 part of fuller olefinic carbon 60 .1；2 10 parts of the polyethylene of maleic anhydride grafting；13 parts of antioxidant；13 parts of plasticizer；12 parts of coupling agent.Two-dimensional graphene, one-dimensional CNT and zero dimension fullerene are mixed to build the antistatic network of three-dimensional carbon material in the present invention, conductive network is built in base polyethylene using the carbon material of less ratio.This composite processing technique is simple, can be mass, and the product obtained by single injection-molded can be applied in antistatic field.
Description
Technical field
It is particularly a kind of common by graphene, CNT and fullerene the present invention relates to macromolecule material preparation area
Modified composite polyethylene material and preparation method thereof.
Background technology
The zero dimension fullerene found in 1989, the one-dimensional CNTs found in 1991 and the two-dimentional graphite found in 2004
Active material in Xi Doushi carbon materials family, this different materials are all " favorites " in researchers eye.These materials
It is respectively provided with good electric conductivity.Representative of the graphene as 21 century new material, its excellent conduction, heat conductivility, machinery
Intensity is also to receive much concern.
Industrial widely used polyethylene is formed by vinyl monomer polymerization, is divided into high density polyethylene (HDPE) and low-density
Polyethylene.Available for preparing film, hollow product, tubing, fiber and container, seal case material etc..The packaging of electronic component
Box is also the extensive application field of polyethylene, due to the high-insulativity of polythene material in itself, is used as the bag of electronic component
Dress field, then Electrostatic Absorption be present in surface, easily cause the danger such as electric shock, sparking.The poly- second of some in carrier
Alkene packing box causes unnecessary loss and danger because the electrostatic on surface can also cause fire.
The content of the invention
It is an object of the present invention to overcome the above-mentioned technical problems, and to provide one kind by graphene, CNT and fullerene
Modified composite polyethylene material and preparation method thereof jointly, by added in insulator polyethylene conductive component carbon material come
Packing box is made to the composite of antistatic body.
The technical scheme for solving above-mentioned technical problem is as follows：
A kind of composite polyethylene material being modified jointly by graphene, CNT and fullerene, by weight, including with
Lower component：
Further, the thickness of described graphene is 1~5 layer, and piece footpath is 5~15 μm, specific surface area 600m2/g。
Further, described CNT is multi-walled carbon nanotube, and a diameter of 6~10nm, length is 10~30 μm.
Further, described fullerene is C60 structures.
Further, antioxidant is the one or more in single phenol, bis-phenol, triphenol.
Further, described plasticizer is in Methyl Benzene-o-dicarboxylate, butyl phthalate, octyl phthalate
One or more.
Further, described coupling agent is the one or more in KH550, KH560, KH570.
The preparation method of the composite, is comprised the following steps that：
(1) graphene, CNT, fullerene are obtained into three's mixture by the scattered stirring of high speed, then with poly- second
Alkene master batch stirs, and is eventually adding each auxiliary agent and obtains mixed material；
(2) by the mixed material that above-mentioned steps (1) obtain in 120~140 DEG C of dry 5~12h；
(3) mixed material of step (2) after drying is sent into double screw extruder extrusion, be granulated by pelleter；
Each area's temperature of described double screw extruder is between 150~170 DEG C, and screw speed is 20~45rpm, feeding
Rotating speed is 8~12rpm, and pelleter rotating speed is 150~190rpm.
The beneficial effects of the present invention are：Two-dimensional graphene, one-dimensional CNT and zero dimension fullerene are mixed in the present invention
Conjunction is ingenious to build the antistatic network of three-dimensional carbon material, and conductive mesh is built in base polyethylene using the carbon material of less ratio
Network.The polyethylene being grafted by maleic anhydride is used as compatilizer, promotes the compound action between polyethylene and carbon material so that
Three-dimensional structure is more stable.This composite processing technique is simple, can be mass, the production obtained by single injection-molded
Product can be applied in antistatic field.
Embodiment
With reference to embodiment, the present invention is further detailed explanation.
Embodiment 1：
Take the graphene of 0.1 mass parts, the multi-walled carbon nanotube of 0.1 mass parts, 0.1 mass parts C60 structures fowler
Alkene, by three kinds of carbon materials by the scattered polypropylene for being uniformly mixed, adding 50 mass parts of high speed, it is well mixed again, most
The maleic anhydride grafted polyethylene of 2 mass parts, single phenolic antioxidant of 1 mass parts, the phthalic acid first of 1 mass parts are added afterwards
The KH550 coupling agents of ester, 1 mass parts.Wherein, the thickness of graphene is 1 layer, and piece footpath is 5 μm, specific surface area 600m2/ g is more
A diameter of 6nm of wall carbon nano tube, length are 10 μm.Then said mixture material is dried into 5 hours at 120 DEG C, be sent into
Extrude in double screw extruder, be granulated with pelleter.Each area's temperature of screw rod is：One 150 DEG C of area, 160 DEG C of 2nd area, 170 DEG C of 3rd area,
Four 170 DEG C of areas, 160 DEG C of 5th area, 150 DEG C of head temperature, screw speed 20rpm, feeding rotating speed are 8rpm, and pelleter rotating speed is
150rpm。
Embodiment 2
Take the graphene of 0.1 mass parts, the multi-walled carbon nanotube of 0.1 mass parts, 0.1 mass parts C60 structures fowler
Alkene, by three kinds of carbon materials by the scattered polypropylene for being uniformly mixed, adding 100 mass parts of high speed, it is well mixed again, most
The maleic anhydride grafted polyethylene of 4 mass parts, the bisphenol antioxidant of 1 mass parts, the phthalic acid fourth of 1 mass parts are added afterwards
The KH560 coupling agents of ester, 1 mass parts.Wherein, the thickness of graphene is 2 layers, and piece footpath is 10 μm, specific surface area 600m2/ g,
A diameter of 7nm of multi-walled carbon nanotube, length are 20 μm.Then said mixture material is dried into 5 hours at 120 DEG C, sent
Enter in double screw extruder and extrude, be granulated with pelleter.Each area's temperature of screw rod is：One 150 DEG C of area, 160 DEG C of 2nd area, three areas 170
DEG C, 170 DEG C of 4th area, 160 DEG C of 5th area, 150 DEG C of head temperature, screw speed 30rpm, feeding rotating speed is 10rpm, and pelleter turns
Speed is 190rpm.
Embodiment 3
Take the graphene of 0.2 mass parts, the multi-walled carbon nanotube of 0.2 mass parts, 0.2 mass parts C60 structures fowler
Alkene, by three kinds of carbon materials by the scattered polypropylene for being uniformly mixed, adding 100 mass parts of high speed, it is well mixed again, most
It is misery that the maleic anhydride grafted polyethylene of 4 mass parts, three phenolic antioxidants of 1 mass parts, the O-phthalic of 1 mass parts are added afterwards
The KH570 coupling agents of ester, 1 mass parts.Wherein, the thickness of graphene is 3 layers, and piece footpath is 15 μm, specific surface area 600m2/ g,
A diameter of 8nm of multi-walled carbon nanotube, length are 30 μm.Then said mixture material is dried into 5 hours at 120 DEG C, sent
Enter in double screw extruder and extrude, be granulated with pelleter.Each area's temperature of screw rod is：One 150 DEG C of area, 160 DEG C of 2nd area, three areas 170
DEG C, 170 DEG C of 4th area, 160 DEG C of 5th area, 150 DEG C of head temperature, screw speed 40rpm, feeding rotating speed is 12rpm, and pelleter turns
Speed is 180rpm.
Embodiment 4
Take the graphene of 0.3 mass parts, the multi-walled carbon nanotube of 0.3 mass parts, 0.3 mass parts C60 structures fowler
Alkene, by three kinds of carbon materials by the scattered polypropylene for being uniformly mixed, adding 100 mass parts of high speed, it is well mixed again, most
The maleic anhydride grafted polyethylene of 6 mass parts, the bisphenol antioxidant of 1 mass parts, the phthalic acid fourth of 1 mass parts are added afterwards
The KH560 coupling agents of ester, 1 mass parts.Wherein, the thickness of graphene is 5 layers, and piece footpath is 10 μm, specific surface area 600m2/ g,
A diameter of 7nm of multi-walled carbon nanotube, length are 20 μm.Then said mixture material is dried into 12 hours at 140 DEG C, sent
Enter in double screw extruder and extrude, be granulated with pelleter.Each area's temperature of screw rod is：One 150 DEG C of area, 160 DEG C of 2nd area, three areas 170
DEG C, 170 DEG C of 4th area, 160 DEG C of 5th area, 150 DEG C of head temperature, screw speed 45rpm, feeding rotating speed is 12rpm, and pelleter turns
Speed is 190rpm.
Embodiment 5
Take the graphene of 1 mass parts, the multi-walled carbon nanotube of 1 mass parts, 1 mass parts C60 structures fullerene, by three
Kind carbon material is well mixed by the scattered polypropylene for being uniformly mixed, adding 80 mass parts of high speed, is eventually adding 10 again
The maleic anhydride grafted polyethylene of mass parts, the bisphenol antioxidant of 3 mass parts, the butyl phthalate of 3 mass parts, 2 matter
Measure the KH560 coupling agents of part.Wherein, the thickness of graphene is 4 layers, and piece footpath is 10 μm, specific surface area 600m2/ g, more wall carbon
A diameter of 10nm of nanotube, length are 25 μm.Then said mixture material is dried into 10 hours at 130 DEG C, be sent into double
Extrude in screw extruder, be granulated with pelleter.Each area's temperature of screw rod is：One 150 DEG C of area, 160 DEG C of 2nd area, 170 DEG C of 3rd area, four
170 DEG C of area, 160 DEG C of 5th area, 150 DEG C of head temperature, screw speed 30rpm, feeding rotating speed are 10rpm, and pelleter rotating speed is
190rpm。
Embodiment 6
Take the graphene of 0.5 mass parts, the multi-walled carbon nanotube of 0.5 mass parts, 0.5 mass parts C60 structures fowler
Alkene, by three kinds of carbon materials by the scattered polypropylene for being uniformly mixed, adding 60 mass parts of high speed, it is well mixed again, most
The maleic anhydride grafted polyethylene of 7 mass parts, the bisphenol antioxidant of 2 mass parts, the phthalic acid fourth of 2 mass parts are added afterwards
The KH570 coupling agents of ester, 2 mass parts.Wherein, the thickness of graphene is 4 layers, and piece footpath is 10 μm, specific surface area 600m2/ g,
A diameter of 10nm of multi-walled carbon nanotube, length are 25 μm.Then said mixture material is dried into 8 hours at 135 DEG C, sent
Enter in double screw extruder and extrude, be granulated with pelleter.Each area's temperature of screw rod is：One 150 DEG C of area, 160 DEG C of 2nd area, three areas 170
DEG C, 170 DEG C of 4th area, 160 DEG C of 5th area, 150 DEG C of head temperature, screw speed 30rpm, feeding rotating speed is 10rpm, and pelleter turns
Speed is 190rpm.
Comparative example 1
Take the polyethylene of 50 mass parts, add the maleic anhydride grafted polyethylenes of 2 mass parts, 1 mass parts antioxidant,
The coupling agent of the plasticizer of 1 mass parts, 1 mass parts.Then above-mentioned raw materials are dried into 5 hours at 120 DEG C, is sent into twin-screw
Extrude in extruder, be granulated with pelleter.Each area's temperature of screw rod is：One 150 DEG C of area, 160 DEG C of 2nd area, 170 DEG C of 3rd area, 4th area
170 DEG C, 160 DEG C of 5th area, 150 DEG C of head temperature, screw speed 20rpm, feeding rotating speed is 10rpm, and pelleter rotating speed is
190rpm。
The measure of performance：
(1) antistatic property is tested：
2min is molded under 10MPa using vulcanizing press, composite sheet is obtained, using high resistant instrument to composite
Specific insulation tested, test voltage 100V.
(2) test result such as following table：
| Specific insulation (Ω cm) | |
| Embodiment 1 | 4.2×108 |
| Embodiment 2 | 1.4×109 |
| Embodiment 3 | 2.7×109 |
| Embodiment 4 | 6.5×108 |
| Embodiment 5 | 1.2×109 |
| Embodiment 6 | 5.4×108 |
| Comparative example 1 | >1014 |
The specific insulation of antistatic body need to be 10 it can be seen from above table7~1010Between Ω cm, it is evident that
Reach the standard of antistatic body by the composite polyethylene material being modified jointly by graphene, CNT and fullerene,
And comparative example 1 is not to be more than 10 by modified polyethylene, its volume resistivity value14, it is evident that it is not meet antistatic body
Standard.
It is described above, be only presently preferred embodiments of the present invention, any formal limitation not done to the present invention, it is every according to
Any simply modification, the equivalent variations made in technical spirit according to the present invention to above example, each fall within the guarantor of the present invention
Within the scope of shield.
Claims (8)
1. a kind of composite polyethylene material being modified jointly by graphene, CNT and fullerene, it is characterised in that by weight
Meter, including following components：
2. the composite polyethylene material according to claim 1 being modified jointly by graphene, CNT and fullerene, its
It is characterised by, the thickness of described graphene is 1~5 layer, and piece footpath is 5~15 μm, specific surface area 600m2/g。
3. the composite polyethylene material according to claim 1 being modified jointly by graphene, CNT and fullerene, its
It is characterised by, described CNT is multi-walled carbon nanotube, and a diameter of 6~10nm, length is 10~30 μm.
4. the composite polyethylene material according to claim 1 being modified jointly by graphene, CNT and fullerene, its
It is characterised by, described fullerene is C60 structures.
5. the composite polyethylene material according to claim 1 being modified jointly by graphene, CNT and fullerene, its
It is characterised by, antioxidant is the one or more in single phenol, bis-phenol, triphenol.
6. the composite polyethylene material according to claim 1 being modified jointly by graphene, CNT and fullerene, its
Be characterised by, described plasticizer be Methyl Benzene-o-dicarboxylate, butyl phthalate, one kind in octyl phthalate or
It is a variety of.
7. the composite polyethylene material according to claim 1 being modified jointly by graphene, CNT and fullerene, its
It is characterised by, described coupling agent is the one or more in KH550, KH560, KH570.
A kind of 8. polyethylene being modified jointly by graphene, CNT and fullerene as described in any one of claim 1~7
The preparation method of composite, it is characterised in that comprise the following steps that：
(1) graphene, CNT, fullerene are obtained into three's mixture by the scattered stirring of high speed, it is then female with polyethylene
Grain stirs, and is eventually adding each auxiliary agent and obtains mixed material；
(2) by the mixed material that above-mentioned steps (1) obtain in 120~140 DEG C of dry 5~12h；
(3) mixed material of step (2) after drying is sent into double screw extruder extrusion, be granulated by pelleter；
Each area's temperature of described double screw extruder is between 150~170 DEG C, and screw speed is 20~45rpm, feeding rotating speed
For 8~12rpm, pelleter rotating speed is 150~190rpm.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201710515921.5A CN107446231A (en) | 2017-06-29 | 2017-06-29 | A kind of composite polyethylene material being modified jointly by graphene, CNT and fullerene and preparation method thereof |
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| CN201710515921.5A CN107446231A (en) | 2017-06-29 | 2017-06-29 | A kind of composite polyethylene material being modified jointly by graphene, CNT and fullerene and preparation method thereof |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107523078A (en) * | 2017-08-01 | 2017-12-29 | 湖北运来塑胶科技有限公司 | Carbon nano-tube filled wood-plastic board of a kind of graphene and preparation method thereof |
| CN111283690A (en) * | 2020-01-16 | 2020-06-16 | 中国科学院重庆绿色智能技术研究院 | Elastic bionic villus type electronic skin for human-computer interaction safety |
| CN114456470A (en) * | 2022-03-09 | 2022-05-10 | 中海石油(中国)有限公司 | Polymer composite material with gas high-barrier property |
| CN115044128A (en) * | 2022-05-24 | 2022-09-13 | 国网冀北电力有限公司电力科学研究院 | Heat exchange polyethylene composite material, preparation thereof and heat exchange plastic pipe prepared from same |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104449010A (en) * | 2014-12-26 | 2015-03-25 | 苏州格瑞丰纳米科技有限公司 | Polymer/graphene anti-static coating, preparation method and application thereof |
| CN105273309A (en) * | 2015-10-26 | 2016-01-27 | 李修兵 | Anti-static and flame-retardant graphene-based polypropylene composite and preparation method thereof |
-
2017
- 2017-06-29 CN CN201710515921.5A patent/CN107446231A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104449010A (en) * | 2014-12-26 | 2015-03-25 | 苏州格瑞丰纳米科技有限公司 | Polymer/graphene anti-static coating, preparation method and application thereof |
| CN105273309A (en) * | 2015-10-26 | 2016-01-27 | 李修兵 | Anti-static and flame-retardant graphene-based polypropylene composite and preparation method thereof |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107523078A (en) * | 2017-08-01 | 2017-12-29 | 湖北运来塑胶科技有限公司 | Carbon nano-tube filled wood-plastic board of a kind of graphene and preparation method thereof |
| CN111283690A (en) * | 2020-01-16 | 2020-06-16 | 中国科学院重庆绿色智能技术研究院 | Elastic bionic villus type electronic skin for human-computer interaction safety |
| CN114456470A (en) * | 2022-03-09 | 2022-05-10 | 中海石油(中国)有限公司 | Polymer composite material with gas high-barrier property |
| CN115044128A (en) * | 2022-05-24 | 2022-09-13 | 国网冀北电力有限公司电力科学研究院 | Heat exchange polyethylene composite material, preparation thereof and heat exchange plastic pipe prepared from same |
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Application publication date: 20171208 |